Silicone polyester resins in personal care applications

ABSTRACT

The present invention relates to the use in personal care products of a series of novel silicone polymers (referred to as polyester silicone resin) that are very useful in a variety of personal care applications including personal care.

FIELD OF THE INVENTION

The present invention relates to the use in personal care products of aseries of novel silicone polymers These polymers are referred to as“Silicone polyester resins” and are covered by U.S. Pat. No. 7,344,708issued Mar. 18, 2008 to LaVay et al. These products have very uniquefilm forming properties that make the compounds very useful in a varietyof personal care applications including personal care. SiliconePolyesters and solvent blends offer a unique spread and texture fortopical applications to skin hair resulting in matte, moderate gloss andhigh gloss properties for oil in water, water in oil. In addition, thesepolyester silicone resin blends also offer a unique spread and texturefor cosmetic applications of face, eye and lips also resulting in Matte,gloss and high gloss properties this is due in part to the ability toalter the refractive index range for the polyester silicone resins aloneand in mixture with solvents. The invention is in the field ofcompositions for application to keratinous surfaces such as eyebrows,eyelashes, eyelids, facial or body skin, lips, or hair for the purposeof coloring, conditioning, or beautifying the keratinous surface.

BACKGROUND OF THE INVENTION

Manufacturers of cosmetic products are on an eternal quest to formulatecosmetic compositions that provide better films on keratinous surfaces.The ideal cosmetic film lasts until the consumer wants to remove it bywashing with water or using remover compositions. At the same time thefilm provides a very natural, aesthetic appearance on the keratinoussurface without looking fake or “made up”. A suitable cosmetic filmshould permit the underlying keratinous surface to breathe, retainmoisture, and exhibit a superficially attractive appearance that is nottoo artificial in appearance.

Most often, polymers are incorporated into cosmetic compositions to formthe cosmetic film. Generally, such polymers contain many repeatingunits, or monomers, that give the polymer substantive, film formingproperties. Such polymers may be natural or synthetic. Natural polymerssuch as cellulosics, gums, and resins, have been used as film formers incosmetics for many years. In more recent years, as polymer chemistry hasadvanced, polymer manufacturers have been able to manufacture a widevariety of synthetic polymers for use in cosmetics. In general,synthetic polymers fall into one of two classes: silicone polymers(based upon silicon and oxygen), or organic polymers comprised ofrepeating organic moieties, for example, polymers obtained bypolymerizing ethylenically unsaturated monomers such as acrylates oralkylenes, optionally with organic moieties such as amides, urethanes,and the like. Certain synthetic polymers that contain both siloxanemonomers and organic moieties are also known.

While synthetic polymers comprised of organic moieties such asethylenically unsaturated monomers are excellent film formers, theysometimes do not exhibit optimal properties on keratinous surfaces suchas skin. Skin is a very dynamic substrate that is in constant movementso cosmetic films that are affixed to skin or lips must exhibit somedegree of plasticity. Synthetic organic polymers do not always exhibitthe necessary plasticity, and will sometimes crack on dynamic keratinoussurfaces such as skin. For this reason, synthetic organic polymers arenot as widely used in cosmetic compositions that are applied to skin.

On the other hand, silicone polymers are excellent film formers and havebeen used to form cosmetic films in many successful commercial products.While silicones provide excellent wear and adhesion in general, organicsynthetic polymers often provide desired surface properties that arelacking in silicones. It has been found that a certain silicone polymer,referred to as polyester silicone resin, when used in cosmeticcompositions, provides excellent substantivity to the composition,promotes formation of a suitable cosmetic film, and provides a light,pleasant feel to the composition.

The term silicone resin has been applied both to and misapplied to avariety of materials over time. Silicone resins as used herein refer toa series of products which include at least two silicone backbones thatare joined by a “crosslinking group”. The number of crosslinking groupsthat are present as a percentage of the total molecular weight willdetermine the properties of the resulting polymer. Quite to thecontrary, our compounds, although the reaction of polyester SiH andpolyester vinyl siloxanes, form elastomeric films when the solvent isremoved. We have no vinyl groups, no silanic hydrogen groups andconsequently are quite surprised that the compounds are film formers.

Our compounds surprisingly and in an unexpected manner are polyestersthat form oil loving films.

The literature contains many patents that deal with silicone resins.Many patents deal with improvements of the resins. However, there areonly a number of classes of resin compounds differing in the nature ofthe crosslinker. One class is the so called “Q resins”.

The oxygen that needs another bond connects to another polymer as shown:

The crosslinking group is —O—. This type of resin is disclosed in U.S.Pat. No. 6,139,823, incorporated herein by reference. This type ofmaterial has a tetrafunctional “Q” group in which the Si has four oxygenatoms attached. This type of resin is very powdery and is rarely usedwithout a plasticizer. This class of compounds can also dry the skin.

The next class of resin contain alkyl connecting groups.

In the case where n=1 a multi functional SiH fluid is hydrosilated witha multifunctional vinyl siloxane. As n is increased the reactant is analpha omega divinyl compound reacted with a multifunctional SiH fluid.

The SiH polymer is crosslinked with the organic divinyl molecule byreacting the vinyl with the SiH groups using the hydrosilation reaction.The reaction is generally run in solvent such as cyclomethicone (D4 orD5 or hexamethyl disiloxane) or in volatile organic like isododecane. Acatalyst, generally a platinum based one, is used to effect thereaction. Chloroplatinic acid or platinum divinyl (commonly referred toas Karstedt) catalyst are preferred. The resulting material is a viscousliquid that when the solvent evaporates provides a film. The commonalityhere is that until the compounds of the present invention it was feltthat all film forming resins had to be crosslinked. Our products refutethat long held position.

United States Patent Application 20040180020 entitled Cosmeticcompositions published Sep. 16, 2004 to Manelski, Jean Marie; et al.,incorporated herein by reference discloses Compositions of the inventioncontaining at least one cyclized dimethicone. The term “cyclizeddimethicone” means an organosiloxane comprised of repeating —[Si—O₂]—,or “D” units, which form one or more cyclized portions in the finalpolymer. The cyclized portions, or rings, are formed by cross linkingcertain portions along the organosiloxane chain to form rings that maybe structurally aligned along the polymeric chain. The claimed polymersare known compounds and are stated to have the INCI name dimethiconecrosspolymer-3) and isododecane; or JEECHEM HPIB which is a mixture ofcyclized dimethicone (dimethicone crosspolymer-3) and hydrogenatedpolyisobutene and cyclomethicone. Unlike the compounds of the presentinvention these polymers are cross linked internally with a carbon basedcross linking agent. The materials are made by the reaction of aninternal silanic hydrogen compound and a divinyl organic. Typical of thereaction is below:

R is —(CH₂)₂—(CH₂)_(n)(CH₂)₂—

The above compounds are referred to as cyclized dimethicone by thereferenced patent application. The cyclization results by the “boxingout” of the silanic hydrogen moiety with the organo functionalityintroduced with the alpha omega divinyl compound. It will be clearlynoted that the compounds so described are not truly dimethicone sincethere are sections of the molecule that are organofunctional. Alsoplease additionally note the branching pattern is internal, that is theorganic functional ring can only occur using non-terminal silanichydrogen compounds.

The compositions of the present invention contain are made byesterification of dimer acid and silicone copolyols. Hydrosilylationreactions are not required.

The fatty nature of the dimer acid and its substantivity to the skin andpigments makes the compounds of the present invention unique in theirproperties.

Our compounds surprisingly and in an unexpected manner are skinsubstantive, soluble in oils and are form films. As previously stated webelieve this is because of interlocking of the cyclic structures. Thesize of the cyclic is controlled by the choice of raw materials. We havesurprisingly found that this pattern results in properties heretoforeunknown in resin technology. None of the compounds of the prior artanticipate or make obvious the film forming properties coupled with theoil solubility seen in the compounds of the present invention.

OBJECT OF THE INVENTION

It is an object of the invention to provide a cosmetic composition withexcellent wear and adhesion to keratinous surfaces.

It is another object of the invention to provide a cosmetic compositionthat provides a composition that exhibits excellent film formingproperties.

It is another object of the invention to provide a mascara thatlengthens, colors, and curls lashes, and exhibits long wearingproperties.

It is another object of the invention to provide a lipstick compositionthat is long wearing and provides a glossy finish.

It is another object of the invention to provide cosmetic compositionsfor application to keratinous surfaces that look natural, provide a richcolor, and exhibit reduced smudging.

Another object of the invention is to provide commercially acceptable,stable, cosmetic products for making up keratinous surfaces.

It is the object of the present invention to apply to the hair and skina series of silicone film forming polymers that have no crosslinkinggroups. The compounds are made by reacting polyester divinyl siliconeand polyester silanic hydrogen compounds.

Another object of the present invention is to provide a series ofproducts suitable for formulation into personal care products includingbut not limited to lipsticks, mascara, hair and skin care compositions.

Other objects of the invention will become clear as one reads thespecification attached hereto.

All charges given herein are % by weight, all temperatures are ° C., allpatents and publications referred to herein are incorporated herein byreference in their entirety as appropriate.

SUMMARY OF THE INVENTION

Disclosed herein is a process for treating hair and skin which comprisescontacting the hair and skin with an effective film formingconcentration of a specific polyester resin. These films are used incosmetic makeup or care composition for the skin, including the scalp,of both the human face and body, the lips or the epidermal derivativesof humans, such as hair, eyelashes, eyebrows and nails, which comprises,in a cosmetically acceptable medium, at least one specific polyester.

The present invention relates to a process for providing a film to thehair and skin which comprises contacting the hair and skin with aneffective film forming concentration of a silicone resins that providefilms that are cosmetically acceptable and are free of crosslinkinggroups.

The compositions of the present invention containing between 0.1 and 50%by weight of the compounds made by reacting specific alpha omegadi-vinyl siloxane compounds with a specific alpha omega di-silanichydrogen containing silicone compounds. The reaction is conducted in asuitable solvent selected from the group consisting of cyclomethicone(D-4 and D-5 and mixtures thereof) and isoalkanes (iso-dodecane).

The invention comprises a cosmetic composition comprising specificsilicone resin solvated or dispersed in a cosmetically acceptablecarrier.

The invention further comprises a cosmetic composition comprising atleast one polyester silicone resin and at least one non-silicone polymerin a cosmetically acceptable carrier.

The invention further comprises a cosmetic composition comprising atleast one polyester silicone resin in combination with at least onesilicone polymer in a cosmetically acceptable carrier.

The invention further comprises a cosmetic composition comprising atleast one polyester silicone resin in combination with at least onepolymer comprised of silicone monomers and organic monomers.

The invention further comprises a cosmetic composition comprising atleast one polyester silicone resin in a cosmetically acceptable waterand oil emulsion carrier.

The invention further comprises a cosmetic composition comprising atleast one polyester silicone resin in an anhydrous cosmeticallyacceptable carrier.

DETAILED DESCRIPTION

The cosmetically acceptable carrier may generally be anhydrous, or inthe form of a water-in-oil or oil-in-water emulsion, the lattercontaining a water phase and an oil phase.

I. The Polyester Silicone Resin

Resins of the present invention are a class of silicone compounds whichare prepared according to the teachings of U.S. Pat. No. 7,344,708incorporated herein by reference.

A polyester made by esterification reaction consisting of reacting:

-   (a) dimer acid conforming to the following structure:

or hydrogenated dimer acid conforming to the following structure:

or mixtures thereof;with

-   (b) a dimethicone copolyol conforming to the following structure:

wherein;

-   a is an integer ranging from 0 to 100;-   b is an integer ranging from 4 to 20, with the proviso that b is    greater than a times 0.75;-   x is an integer ranging from 6 to 20;-   with the proviso that the ratio of hydroxyl group to acid group be    between 0.7 and 1.4.

The products can be diluted in a solvent, either volatile silicone(cyclomethicone (D4 or D5 or mixtures thereof) or hydrocarbon solventlike isododecane.

One type of cosmetic composition of the present invention is colorcosmetics designed to provide improved transfer resistance comprising:

-   a) 1-70% of a volatile solvent having a viscosity of about 0.5 to 20    centipoise at 25° C. and selected from the group consisting of    volatile silicones, C. 8-20 isoparaffins, and mixtures thereof,-   b) 0.1-15% of the silicone polyester resins of U.S. Pat. No.    7,344,708.-   c) 10-45% of a wax selected from the group consisting of synthetic    wax, ceresin, paraffin, ozokerite, illipe butter, beeswax, carnauba,    microcrystalline, lanolin, candelilla, cocoa butter, shellac wax,    spermaceti, bran wax, capok wax, sugar cane wax, montan wax, whale    wax, bayberry wax, and mixtures thereof,-   d) 5-50% of a powder component which is a dry, particulate matter    comprised of pigments and powders having a particle size of 0.02 to    50 microns wherein the pigment to powder weight ratio ranges from    1:20 to 20:1, and-   e) 1-30% oil,

The cosmetic composition in accordance with the invention may contain avariety of other ingredients including film forming polymers, pigments,waxes, oils, vitamins, and so on. Examples of such other ingredientsinclude those described below.

A. Pigments

The composition of the invention may comprise about 0.05-30%, preferablyabout 0.1-25%, more preferably about 0.5-20% by weight of the totalcomposition of one or more pigments which may be organic or inorganic.Examples of organic pigment families that may be used herein includeazo, (including monoazo and diazo), fluoran, xanthene, indigoid,triphenylmethane, anthroquinone, pyrene, pyrazole, quinoline, quinoline,or metallic salts thereof. Preferred are D&C colors, FD&C colors, orLakes of D&C or FD&C colors. The term “D&C” means drug and cosmeticcolors that are approved for use in drugs and cosmetics by the FDA. Theterm “FD&C” means food, drug, and cosmetic colors which are approved foruse in foods, drugs, and cosmetics by the FDA. Certified D&C and FD&Ccolors are listed in 21 CFR 74.101 et seq. and include the FD&C colorsBlue 1, Blue 2, Green 3, Orange B, Citrus Red 2, Red 3, Red 4, Red 40,Yellow 5, Yellow 6, Blue 1, Blue 2; Orange B, Citrus Red 2; and the D&Ccolors Blue 4, Blue 9, Green 5, Green 6, Green 8, Orange 4, Orange 5,Orange 10, Orange 11, Red 6, Red 7, Red 17, Red 21, Red 22, Red 27, Red28, Red 30, Red 31, Red 33, Red 34, Red 36, Red 39, Violet 2, Yellow 7,Yellow 8, Yellow 10, Yellow 11, Blue 4, Blue 6, Green 5, Green 6, Green8, Orange 4, Orange 5, Orange 10, Orange 11, and so on. Suitable Lakesof D&C and FD&C colors are defined in 21 CFR 82.51. Particularlypreferred are Lakes formed by the reaction of the organic pigment with ametallic salt such as aluminum, calcium, zirconium, barium, and thelike. Suitable reds include pigments from the monoazo, disazo, fluoran,xanthene, or indigoid families or Lakes thereof, such as Red 4, 6, 7,17, 21, 22, 27, 28, 30, 31, 33, 34, 36, and Red 40. Also suitable areLakes of such red pigments. Typically the metal salts are aluminum,barium, and the like.

Suitable yellows include those where the yellow pigment is a pyrazole,monoazo, fluoran, xanthene, quinoline, or salt thereof, such as Yellow5, 6, 7, 8, 10, and 11, as well as Lakes of such yellow pigments.

Suitable violets include those from the anthroquinone family, such asViolet 2 and Lakes thereof. Examples of orange pigments are Orange 4, 5,10, 11, or Lakes thereof.

Suitable inorganic pigments include iron oxides such as red, blue,black, green, and yellow; titanium dioxide, bismuth oxychloride, and thelike. Preferred are iron oxides. The iron oxides may be treated withhydrophobic agents such as silicone, lecithin, mineral oil, or similarmaterials, will cause the pigment to be hydrophobic or lipophilic innature, exhibiting an affinity for oily phase ingredients.

B. Particulate Fillers

The composition may contain one or more particulate fillers, which aregenerally non-pigmentitious powdery materials. If so, suggested rangesare about 0.001-40%, preferably about 0.05-35%, more preferably about0.1-30% by weight of the total composition. Preferably, the particulatefillers have particle sizes ranging from about 0.02 to 100, preferably0.5 to 100, microns. Suitable particle fillers include titanated mica,fumed silica, spherical silica, polymethylmethacrylate, micronizedteflon, boron nitride, acrylate copolymers, aluminum silicate, aluminumstarch octenylsuccinate, bentonite, calcium silicate, cellulose, chalk,corn starch, diatomaceous earth, fuller's earth, glyceryl starch,hectorite, hydrated silica, kaolin, magnesium aluminum silicate,magnesium trisilicate, maltodextrin, montmorillonite, microcrystallinecellulose, rice starch, silk powder, silica, talc, mica, zinc laurate,zinc myristate, zinc rosinate, alumina, attapulgite, calcium carbonate,calcium silicate, dextran, kaolin, nylon, silica silylate, sericite, soyflour, tin oxide, titanium hydroxide, trimagnesium phosphate, walnutshell powder, or mixtures thereof. The above mentioned powders may besurface treated with lecithin, amino acids, mineral oil, silicone oil orvarious other agents either alone or in combination, which coat thepowder surface and render the particles more lipophilic in nature.

C. Oils

The composition may contain one or more oils, and if so in ranges fromabout 0.1-95%, preferably about 5-80%, more preferably about 10-75% byweight of the total composition. The term “oil” means a material that isa pourable liquid at room temperature. A variety of such oils aresuitable including volatile oils, nonvolatile oils, and mixturesthereof.

1. Volatile Oils

The term “volatile” means that the oil has a measurable vapor pressure,or a vapor pressure of at least about 2 mm. of mercury at 20° C. Theterm “nonvolatile” means that the oil has a vapor pressure of less thanabout 2 mm. of mercury at 20° C. Suitable volatile oils generally have aviscosity of about 0.5 to 10 centipoise at 25° C. and include polyestersilicones, cyclic silicones, paraffinic hydrocarbons, or mixturesthereof.

(a). Volatile Silicones

Cyclic silicones (or cyclomethicones) are compounds of commerce.

where n=3-6.

Polyester volatile silicones in accordance with the invention have thegeneral formula:

(CH₃).₃—Si—O—[Si(CH.₃)₂—O]_(n)—Si(CH₃)₃

where n=0-7, preferably 0-5.

Polyester and cyclic volatile silicones are available from variouscommercial sources including Siltech LLC, Dow Corning Corporation andGeneral Electric. The Dow Corning volatile silicones are sold under thetradenames Dow Corning 244, 245, 344, and 200 fluids. These fluidscomprise octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,hexamethyldisiloxane, and mixtures thereof.

(b). Paraffinic Hydrocarbons

Also suitable as the volatile oil are various straight or branched chainparaffinic hydrocarbons having 5 to 40 carbon atoms, more preferably8-20 carbon atoms. Suitable hydrocarbons include pentane, hexane,heptane, decane, dodecane, tetradecane, tridecane, and C₈₋₂₀isoparaffins as disclosed in U.S. Pat. Nos. 3,439,088 and 3,818,105,both of which are hereby incorporated by reference. Preferred volatileparaffinic hydrocarbons have a molecular weight of 70-225, preferably160 to 190 and a boiling point range of 30 to 320, preferably 60-260°C., and a viscosity of less than 10 cs. at 25° C. Such paraffinichydrocarbons are available from EXXON under the ISOPARS trademark, andfrom the Permethyl Corporation. Suitable C₁₂ isoparaffins aremanufactured by Permethyl Corporation under the tradename Permethyl 99A.Another C₁₂ isoparaffin (isododecane) is distributed by Presperse underthe tradename Permethyl 99A. Various C₁₆ isoparaffins commerciallyavailable, such as isohexadecane (having the tradename Permethyl R), arealso suitable.

2. Nonvolatile Oils

The composition may also comprise one or more non-volatile liquid oilssuch as silicones, esters, and the like. In the case where it is desiredto make long wearing cosmetic products, if the nonvolatile oils are tooheavy or greasy it may hamper the long wearing characteristics of theinvention. In such a case, the viscosity of the nonvolatile oils, ifpresent, should range from about 11-1000, preferably less than 100centipoise, most preferably less than about 50 centipoise at 25° C.Examples of such oils include polyalkylsiloxanes, polyarylsiloxanes, andpolyethersiloxanes. Examples of such nonvolatile silicones are disclosedin Cosmetics, Science and Technology 27-104 (Balsam and Sagarin ed.1972); and U.S. Pat. Nos. 4,202,879 and 5,069,897, both of which arehereby incorporated by references. Further nonlimiting examples of suchsilicones include dimethicone, phenyl trimethicone, dimethiconecopolyol, and so on.

Also suitable are lower viscosity organic liquids including saturated orunsaturated, substituted or unsubstituted branched or polyester orcyclic organic compounds that are liquid under ambient conditions.Preferred organic liquids include those described in U.S. Pat. Nos.5,505,937; 5,725,845; 5,019,375; and 6,214,329, all of which areincorporated by reference herein in their entirety.

If desired, the claimed composition may contain one or more nonvolatileoils. Such oils generally have a viscosity of greater than 10 centipoiseat 25° C., and may range in viscosity up to 1,000,000 centipoise at 25°C. Such nonvolatile oils are preferably liquid at room temperature (e.g.25° C.), and include those set forth below. In the event long-wearing ortransfer resistant compositions are desired, if non-volatile oils arepresent, they are preferably of lower viscosity, e.g. ranging from about10 to 100,000, preferably 10-50,000, more preferably 10-1000 centipoiseat room temperature. Further examples of non volatile oils include thoseset forth below.

(a). Esters

Suitable esters are mono-, di-, and triesters. The composition maycomprise one or more esters selected from the group, or mixturesthereof.

(i). Monoesters

Monoesters are defined as esters formed by the reaction of amonocarboxylic acid having the formula R—COOH, wherein R is a straightor branched chain saturated or unsaturated alkyl having 2 to 30 carbonatoms, or phenyl; and an alcohol having the formula R—OH wherein R is astraight or branched chain saturated or unsaturated alkyl having 2-30carbon atoms, or phenyl. Both the alcohol and the acid may besubstituted with one or more hydroxyl groups, and in one preferredembodiment of the invention the acid is an alpha hydroxy acid. Eitherone or both of the acid or alcohol may be a “fatty” acid or alcohol, ie.may have from about 6 to 22 carbon atoms. Examples of monoester oilsthat may be used in the compositions of the invention include hexyldecylbenzoate, hexyl laurate, hexadecyl isostearate, hexydecyl laurate,hexyldecyl octanoate, hexyldecyl oleate, hexyldecyl palmitate,hexyldecyl stearate, hexyldodecyl salicylate, hexyl isostearate, butylacetate, butyl isostearate, butyl oleate, butyl octyl oleate, cetylpalmitate, ceyl octanoate, cetyl laurate, cetyl lactate, isostearylisononanoate, cetyl isononanoate, cetyl stearate, stearyl lactate,stearyl octanoate, stearyl heptanoate, stearyl stearate, and so on. Itis understood that in the above nomenclature, the first term indicatesthe alcohol and the second term indicates the acid in the reaction, i.e.stearyl octanoate is the reaction product of stearyl alcohol andoctanoic acid.

(ii). Diesters

Suitable diesters that may be used in the compositions of the inventionare the reaction product of a dicarboxylic acid and an aliphatic oraromatic alcohol. The dicarboxylic acid may contain from 2 to 30 carbonatoms, and may be in the straight or branched chain, saturated orunsaturated form. The dicarboxylic acid may be subsituted with one ormore hydroxyl groups. The aliphatic or aromatic alcohol may also contain2 to 30 carbon atoms, and may be in the straight or branched chain,saturated, or unsaturated form. The aliphatic or aromatic alcohol may besubstituted with one or more substitutents such as hydroxyl. Preferably,one or more of the acid or alcohol is a fatty acid or alcohol, i.e.contains 14-22 carbon atoms. The dicarboxylic acid may also be an alphahydroxy acid. Examples of diester oils that may be used in thecompositions of the invention include diisostearyl malate, neopentylglycol dioctanoate, dibutyl sebacate, di-C₁₂₋₁₃alkyl malate, dicetearyldimer dilinoleate, dicetyl adipate, diusocetyl adipate, diisononyladipate, diisostearyl dimer dilinoleate, disostearyl fumarate,diisostearyl malate, and so on.

(iii). Triesters

Suitable triesters comprise the reaction product of a tricarboxylic acidand an aliphatic or aromatic alcohol. As with the mono- and diestersmentioned above, the acid and alcohol contain 2 to 30 carbon atoms, andmay be saturated or unsatured, straight or branched chain, and, may besubstituted with one or more hydroxyl groups. Preferably, one or more ofthe acid or alcohol is a fatty acid or alcohol containing 14 to 22carbon atoms. Examples of triesters include triarachidin, tributylcitrate, triisostearyl citrate, tri C12-13 alkyl citrate, tricaprylin,tricaprylyl citrate, tridecyl behenate, trioctyldodecyl citrate,tridecyl behenate, tridecyl cocoate, tridecyl isononanoate, and so on.

(b). Hydrocarbon Oils.

It may be desirable to incorporate one or more non-volatile hydrocarbonoils into the claimed composition. The term “nonvolatile” means that theoil has a vapor pressure of less than about 2 mm. of mercury at 20° C.

Suitable nonvolatile hydrocarbon oils include isoparaffins and olefinshaving greater than 20 carbon atoms. Examples of such hydrocarbon oilsinclude C₂₄₋₂₈ olefins, C₃₀₋₄₅ olefins, C₂₀₋₄₀ isoparaffins,hydrogenated polyisobutene, mineral oil, pentahydrosqualene, squalene,squalane, and mixtures thereof.

(c). Lanolin Oil

Also suitable for use in the composition is lanolin oil or derivativesthereof containing hydroxyl, alkyl, or acetyl groups, such ashydroxylated lanolin, isobutylated lanolin oil, acetylated lanolin,acetylated lanolin alcohol, and so on.

(d). Glyceryl Esters of Fatty Acids

The nonvolatile oil may also comprise naturally occurring glycerylesters of fatty acids, or triglycerides. Both vegetable and animalsources may be used. Examples of such oils include castor oil, lanolinoil, C₁₀₋₁₈ triglycerides, caprylic/capric/triglycerides, coconut oil,corn oil, cottonseed oil, linseed oil, mink oil, olive oil, palm oil,illipe butter, rapeseed oil, soybean oil, sunflower seed oil, walnutoil, and the like.

Also suitable as the oil are synthetic or semi-synthetic glycerylesters, e.g. fatty acid mono-, di-, and triglycerides which are naturalfats or oils that have been modified, for example, acetylated castoroil, or mono-, di- or triesters of polyols such as glyceryl stearate,diglyceryl diiosostearate, polyglyceryl-4 isostearate, polyglyceryl-6ricinoleate, glyceryl dioleate, glyceryl diisotearate, glyceryltrioctanoate, diglyceryl distearate, glyceryl linoleate, glycerylmyristate, glyceryl isostearate, PEG castor oils, PEG glyceryl oleates,PEG glyceryl stearates, PEG glyceryl tallowates, and so on.

(e). Nonvolatile Silicones

Nonvolatile silicone oils, both water soluble and water insoluble, arealso suitable for use as the non-volatile oil. Such silicones preferablyhave a viscosity ranging from about 10 to 600,000 centistokes,preferably 20 to 100,000 centistokes at 25° C. Suitable water insolublesilicones include amine functional silicones such as amodimethicone;phenyl substituted silicones such as bisphenylhexamethicone, phenyltrimethicone, or polyphenylmethylsiloxane; dimethicone, alkylsubstituted dimethicones, and mixtures thereof.

Water soluble, non-film forming silicones such as dimethicone copolyol,dimethiconol, and the like may be used. Such silicones are availablefrom Dow Corning as the 3225C formulation aid, Dow 190 and 193 fluids,or similar products marketed by Goldschmidt under the ABIL tradename andSiltech LLC under the Silube tradename.

Also suitable as the oil are various fluorinated oils such asfluorinated silicones, fluorinated esters, or perfluropolyethers.Particularly suitable are fluorosilicones such as trimethylsilylendcapped fluorosilicone oil, polytrifluoropropylmethylsiloxanes, andsimilar silicones such as those disclosed in U.S. Pat. No. 5,118,496which is hereby incorporated by reference. Perfluoropolyethers likethose disclosed in U.S. Pat. Nos. 5,183,589, 4,803,067, 5,183,588 all ofwhich are hereby incorporated by reference, which are commerciallyavailable from Montefluos under the trademark Fomblin, are also suitableshine enhancers.

(f). Fluoroguerbet Esters

Fluoroguerbet esters are also suitable oils. The term “guerbet ester”means an ester which is formed by the reaction of a guerbet alcohol.Guerbet alcohols are well known in the art. One specific type is asfollows:

and a fluoroalcohol having the following general formula:

CF₃—(CF₂)_(n)—CH₂—CH₂—OH

wherein n is from 3 to 40.

with a carboxylic acid having the general formula:

R′COOH,

or

HOOC—R′—COOH

wherein R′ is a straight or branched chain alkyl.

Preferably, the guerbet ester is a fluoro-guerbet ester which is formedby the reaction of a guerbet alcohol and carboxylic acid (as definedabove), and a fluoroalcohol having the following general formula:

CF₃—(CF2)._(n)—CH.₂—CH₂—OH

wherein n is from 3 to 40.

Examples of suitable fluoro guerbet esters are set forth in U.S. Pat.No. 5,488,121 to O'Lenick, which is hereby incorporated by reference.Suitable fluoro-guerbet esters are also set forth in U.S. Pat. No.5,312,968 which is hereby incorporated by reference. One type of such anester is fluorooctyldodecyl meadowfoamate, sold under the tradenameSilube GME-F by Siltech LLC, Dacula Ga.

D. Additional Film Forming Polymers

The composition may contain one or more film forming polymers inaddition to the polyester silicone resin, and if so, ranges of about0.1-35%, preferably 0.5-30%, more preferably 1-25% by weight of thetotal composition of one or more film forming polymers. The film formingpolymer (or film former) may be water soluble or water insoluble.Suitable film forming polymers are those that, when the composition isapplied to the desired surface, form a film on the surface to which thecomposition is applied when the liquid in the composition evaporates.This causes the film forming polymer to form a film which holds theother active ingredients in place with the network created by thehardened polymer. The term “soluble” means that the film forming polymeris soluble in the phase in question, and will form a single homogeneousphase when incorporated therein. For example, if the film formingpolymer is oil soluble it will generally be soluble in the oil phase ofthe composition and when incorporated therein the oil and the polymerwill form a single homogeneous phase with the oily phase ingredients.Similarly, if the film forming polymer is water soluble, if incorporatedin the water phase the polymer and the water will form a singlehomogeneous phase. In the case where the compositions of the inventionare in the emulsion form, it may also be possible for the emulsion tocontain a film forming polymer that is soluble in one phase but is founddispersed in the other phase. For example, water soluble film formingpolymer may be dispersed in the oil phase of the emulsion or an oilsoluble polymer may be dispersed in the water phase of the emulsion. Inshort, any combination of film forming polymer and phase is suitable solong as the compositions are stable. The term “dispersible” means thatthe film forming polymer is readily dispersed in the liquid vehicle andforms a stable, heterogeneous composition where the dispersed polymerremains stable and suspended in the liquid vehicle and is compatibletherewith (without settling out, for example).

A variety of film forming polymers may be suitable. Such polymers may benatural or synthetic and are further described below.

1. Synthetic Polymers

(a). Copolymers of Silicone and Organic Moieties

One type of film forming polymer that may be used in the compositions ofthe invention is obtained by reacting silicone moieties withethylenically unsaturated monomers. These copolymers may be watersoluble or oil soluble depending on the substituents that are found onthe polymer. The resulting copolymers may be graft or block copolymers.The term “graft copolymer” is familiar to one of ordinary skill inpolymer science and is used herein to describe the copolymers whichresult by adding or “grafting” polymeric side chain moieties (i.e.“grafts”) onto another polymeric moiety referred to as the “backbone”.The backbone may have a higher molecular weight than the grafts. Thus,graft copolymers can be described as polymers having pendant polymericside chains, and which are formed from the “grafting” or incorporationof polymeric side chains onto or into a polymer backbone. The polymerbackbone can be a homopolymer or a copolymer. The graft copolymers arederived from a variety of monomer units.

One type of polymer that may be used as the film forming polymer is avinyl-silicone graft or block copolymer. Such material is outlines inU.S. Patent Publication 2004/0180020A1 published Sep. 16, 2004 paragraph[0082] to [0094] incorporated herein by reference.

Another type of such a polymer comprises a vinyl, methacrylic, oracrylic backbone with pendant siloxane groups and pendant fluorochemicalgroups. Such polymers preferably comprise comprise repeating A, C, D andoptionally B monomers. Such material is outlines in U.S. PatentPublication 2004/0180020A1 published Sep. 16, 2004 paragraph [0095] to[0107] incorporated herein by reference.

Such polymers and their manufacture are disclosed in U.S. Pat. Nos.5,209,924 and 4,972,037, which are hereby incorporated by reference.These polymers maybe water soluble or oil soluble depending on thepolymeric substituents.

Another suitable silicone acrylate copolymer is a polymer having avinyl, methacrylic, or acrylic polymeric backbone with pendant siloxanegroups. Such polymers as disclosed in U.S. Pat. Nos. 4,693,935,4,981,903, 4,981,902, and which are hereby incorporated by reference.Preferably, these polymers are comprised of A, C, and optionally Bmonomers are outlined in U.S. Patent Publication 2004/0180020A1published Sep. 16, 2004 paragraph [0109] to [0122] incorporated hereinby reference.

Examples of other suitable copolymers that may be used herein, and theirmethod of manufacture, are described in detail in U.S. Pat. No.4,693,935, Mazurek, U.S. Pat. No. 4,728,571, and Clemens et al., both ofwhich are incorporated herein by reference. Additional grafted polymersare also disclosed in EPO Application 90307528.1, published as EPOApplication 0 408 311, U.S. Pat. No. 5,061,481, Suzuki et al., U.S. Pat.No. 5,106,609, Bolich et al., U.S. Pat. No. 5,100,658, Bolich et al.,U.S. Pat. No. 5,100,657, Ansher-Jackson, et al., U.S. Pat. No.5,104,646, Bolich et al., U.S. Pat. No. 5,618,524, issued Apr. 8, 1997,all of which are incorporated by reference herein in their entirety.

(b). Polymers from Ethylenically Unsaturated Monomers

Also suitable for use as film forming polymers are polymers made bypolymerizing one or more ethylenically unsaturated monomers either aloneor in combination with various types of organic groups, including butnot limited to urethane, amides, polypropylene glycols, etc. The finalpolymer may be a homopolymer, copolymer, terpolymer, or graft or blockcopolymer, and may contain monomeric units such as acrylic acid,methacrylic acid or their simple esters, styrene, ethylenicallyunsaturated monomer units such as ethylene, propylene, butylene, etc.,vinyl monomers such as vinyl chloride, styrene, and so on. Such polymersmay be water soluble or dispersible, or oil soluble or dispersible inoil.

One type of suitable polymer includes those which contain monomers whichare esters of acrylic acid or methacrylic acid, including aliphaticesters of methacrylic acid like those obtained with the esterificationof methacrylic acid or acrylic acid with an aliphatic alcohol of 1 to30, preferably 2 to 20, more preferably 2 to 8 carbon atoms. If desired,the aliphatic alcohol may have one or more hydroxy groups. Also suitableare methacrylic acid or acrylic acid esters esterified with moietiescontaining alicyclic or bicyclic rings such as cyclohexyl or isobornyl,for example.

The ethylenically unsaturated monomer may be mono-, di-, tri-, orpolyfunctional as regards the addition-polymerizable ethylenic bonds. Avariety of ethylenically unsaturated monomers are suitable.

Examples of suitable monofunctional ethylenically unsaturated monomersare material outlined in U.S. Patent Publication 2004/0180020A1published Sep. 16, 2004 paragraph [0129] to [0144] incorporated hereinby reference.

The polymers used in the compositions of the invention can be preparedby conventional free radical polymerization techniques in which themonomer, solvent, and polymerization initiator are charged over a 1-24hour period of time, preferably 2-8 hours, into a conventionalpolymerization reactor in which the constituents are heated to about60-175° C., preferably 80-100° C. The polymers may also be made byemulsion polymerization or suspension polymerization using conventionaltechniques. Also anionic polymerization or Group Transfer Polymerization(GTP) is another method by which the copolymers used in the inventionmay be made. GTP is well known in the art and disclosed in U.S. Pat.Nos. 4,414,372; 4,417,034; 4,508,880; 4,524,196; 4,581,428; 4,588,795;4,598,161; 4,605,716; 4,605,716; 4,622,372; 4,656,233; 4,711,942;4,681,918; and 4,822,859; all of which are hereby incorporated byreference.

(c). Silicone Polymers

Also suitable are various types of water soluble or water insoluble (oilsoluble) high molecular weight silicone polymers such as silicone gums,resins, and the like.

Suitable silicone resins include siloxy silicate polymers having thefollowing general formula:

[(RR′R″)₃SiO_(1/2)]._(x)[SiO.₂]._(y)

wherein R, R′ and R″ are each independently a C₁₋₁₀ straight or branchedchain alkyl or phenyl, and x and y are such that the ratio of(RR′R″)₃SiO_(1/2) units to SiO.₂ units is 0.5 to 1 to 1.5 to 1.

Preferably R, R′ and R″ are a C₁₋₆ alkyl, and more preferably are methyland x and y are such that the ratio of (CH₃).₃SiO_(1/2) units to SiO₂units is 0.75 to 1. Most preferred is this trimethylsiloxy silicatecontaining 2.4 to 2.9 weight percent hydroxyl groups which is formed bythe reaction of the sodium salt of silicic acid, chlorotrimethylsilane,and isopropyl alcohol. The manufacture of triethylsiloxy silicate is setforth in U.S. Pat. Nos. 2,676,182; 3,541,205; and 3,836,437, all ofwhich are hereby incorporated by reference. Trimethylsiloxy silicate asdescribed is available from Dow Corning Corporation under the tradename749 FLuid, which is a blend of about 40-60% volatile silicone and 40-60%trimethylsiloxy silicate. Dow Corning 749 fluid in particular, is afluid containing about 50% trimethylsiloxy silicate and about 50%cyclomethicone. The fluid has a viscosity of 200-700 centipoise at 25°C., a specific gravity of 1.00 to 1.10 at 25° C., and a refractive indexof 1.40-1.41. A similar siloxysilicate resin is available from GESilicones under the tradename SR1000 and is a fine particulate solidmaterial.

Another type of silicone resin is referred to as a T or MT resin, andhas the general formula:

(R₁SiO_(3/2))._(x)

where x ranges from about 1 to 100,000, preferably about 1-50,000, morepreferably about 1-10,000, and wherein R₁ is independently C₁₋₃₀,preferably C.₁₋₁₀, more preferably C₁₋₄ straight or branched chainalkyl, which may be substituted with phenyl or one or more hydroxylgroups; phenyl; alkoxy (preferably C₁₋₂₂, more preferably C.₁₋₆); orhydrogen. Typically T or MT silicones are referred to assilsesquioxanes, and in the case where M units are presentmethylsilsesquioxanes. One type of such resin is manufactured by WackerChemie under the Resin MK designation. This polysilsesquioxane is apolymer comprise of T units and, optionally one or more D (preferablydimethylsiloxy) units. This particularly polymer may have ends cappedwith ethoxy groups, and/or hydroxyl groups, which may be due to how thepolymers are made, e.g. condensation in aqueous or alcoholic media.Other suitable polysilsesquioxanes that may be used as the film formingpolymer include those manufactured by Shin-Etsu Silicones and includethe “KR” series, e.g. KR-220L, 242A, and so on. These particularsilicone resins may contain endcap units that are hydroxyl or alkoxygroups which may be present due to the manner in which such resins aremanufactured.

Another type of silicone resin suitable for use in the inventioncomprises the silicone esters set forth in U.S. Pat. No. 5,725,845 whichis hereby incorporated by reference in its entirety. Other polymers thatcan enhance adhesion to skin include silicone esters comprising units ofthe general formula disclosed in U.S. Patent Publication 2004/0180020A1published Sep. 16, 2004 paragraph [0152] to [0153] incorporated hereinby reference.

Preferably the silicone ester will have a melting point of no higherthan about 90° C. It can be a liquid or solid at room temperature.Preferably it will have a waxy feel and a molecular weight of no morethan about 100,000 Daltons.

Silicone esters having the above formula are disclosed in U.S. Pat. No.4,725,658 and U.S. Pat. No. 5,334,737, which are hereby incorporated byreference. Preferred silicone esters are the liquid siloxy silicatesdisclosed in U.S. Pat. No. 5,334,737, e.g. diisostearoyltrimethylolpropane siloxysilicate (prepared in Examples 9 and 14 of thispatent), and dilauroyl trimethylolpropane siloxy silicate (prepared inExample 5 of the patent), which are commercially available from GeneralElectric under the tradenames SF 1318 and SF 1312, respectively.

Silicone gums or other types of silicone solids may be used providedthey are soluble in the liquid vehicle. Examples of silicone gumsinclude those set forth in U.S. Pat. No. 6,139,823, which is herebyincorporated by reference. Preferred gums have a 600,000 to 1,000,000centipoise at 25° C.

2. Natural Polymers

Also suitable for use are one or more naturally occurring water solubleor oil soluble polymeric materials such as resinous plant extractsincluding such as rosin, shellac, and the like.

E. Plasticizers

It may be desirable to incorporate one more plasticizers into thecomposition. Plasticizers may improve the spreadability and applicationof the composition to the surface to which it is applied and in somecases will interact with the film forming polymer to make it moreflexible. If present, the plasticizer may be found in the oil or waterphase if the composition of the invention is in the form of an emulsion,and in the oil or lipophilic phase if the composition is in theanhydrous °form. Suggested ranges of plasticizers range from about0.01-20%, preferably about 0.05-15%, more preferably about 0.1-10% byweight of the total composition. A variety of plasticizers are suitableincluding Suitable plasticizers include glyceryl, glycol, and citrateesters as disclosed in U.S. Pat. No. 5,066,484, which is herebyincorporated by reference. Examples of such esters include glyceryltribenzoate, glyceryl triacetate, acetyl tributyl citrate, dipropyleneglycol dibenzoate, and the like.

F. Viscosity Modifiers

It may also be desirable to include one or more viscosity modifiers orthickeners in the composition. Suggested ranges of such viscositymodifiers are about 0.01-60%, preferably about 0.05-50%, more preferablyabout 0.1-45% by weight of the total composition.

One type of viscosity modifier includes natural or syntheticmontmorillonite minerals such as hectorite, bentonite, and quaternizedderivatives thereof which are obtained by reacting the minerals with aquaternary ammonium compound, such as stearalkonium bentonite,hectorites, quaternized hectorites such as Quaternium-18 hectorite,attapulgite, carbonates such as propylene carbonate, bentones, and thelike. Particularly preferred is Quaternium-18 hectorite.

Also suitable as the viscosity modifier are various polymeric compoundsknown in the art as associative thickeners. Suitable associativethickeners generally contain a hydrophilic backbone and hydrophobic sidegroups. Examples of such thickeners include polyacrylates withhydrophobic side groups, cellulose ethers with hydrophobic side groups,polyurethane thickeners. Examples of hydrophobic side groups are longchain alkyl groups such as dodecyl, hexadecyl, or octadecyl; alkylarylgroups such as octylphenyl or nonyphenyl

Another type of viscosity modifier that may be used in the compositionsare silicas, silicates, silica silylate, and derivatives thereof. Thesesilicas and silicates are generally found in the particulate form.Particularly preferred is silica.

The viscosity modifers may also be water soluble or water insoluble(e.g. oil soluble) and form part of the oil phase or the water phase.

Also suitable as viscosity modifiers are one or more waxes. A variety ofwaxes are suitable including animal, vegetable, mineral, or siliconewaxes. Generally such waxes have a melting point ranging from about 28to 125° C., preferably about 30 to 100° C. Examples of waxes includeacacia, beeswax, ceresin, cetyl esters, flower wax, citrus wax, carnaubawax, jojoba wax, japan wax, polyethylene, microcrystalline, rice bran,lanolin wax, mink, montan, bayberry, ouricury, ozokerite, palm kernelwax, paraffin, avocado wax, apple wax, shellac wax, clary wax, spentgrain wax, candelilla, grape wax, and polyalkylene glycol derivativesthereof such as PEG6-20 beeswax, or PEG-12 carnauba wax.

Also suitable are various types of silicone waxes, referred to as alkylsilicones, which are polymers that comprise repeating dimethylsiloxyunits in combination with one or more methyl-long chain alkyl siloxyunits wherein the long chain alkyl is generally a fatty chain thatprovides a wax-like characteristic to the silicone. Such siliconesinclude, but are not limited to stearoxydimethicone, behenoxydimethicone, stearyl dimethicone, cetearyl dimethicone, and so on.Suitable waxes are set forth in U.S. Pat. No. 5,725,845, which is herebyincorporated by reference in its entirety. Preferred ranges of wax arefrom about 0.01-75%, preferably about 1-65% by weight of the totalcomposition.

G. Surfactants

The compositions of the invention may comprise about 0.01-20%,preferably about 0.1-15%, more preferably about 0.5-10% by weight of thetotal composition of a surfactant. Surfactants may be used in bothanhydrous and emulsion based compositions. The surfactant may benonionic, although if the composition is in the form of a shampoo orconditioner it will preferably contain anionic or cationic surfactants,respectively.

Suitable nonionic surfactants or emulsifiers include alkoxylatedalcohols, or ethers, formed by the reaction of an alcohol with analkylene oxide, usually ethylene or propylene oxide. Preferably thealcohol is a fatty alcohol having 6 to 30 carbon atoms. Examples of suchingredients include Beheneth 5-30, which is formed by the reaction ofbehenyl alcohol and ethylene oxide where the number of repeated ethyleneoxide units is 5 to 30; Ceteareth 2-100, formed by the reaction of amixture of cetyl and stearyl alcohol with ethylene oxide, where thenumber of repeating ethylene oxide units in the molecule is 2 to 100;Ceteth 1-45 which is formed by the reaction of cetyl alcohol andethylene oxide, and the number of repeating ethylene oxide units is 1 to45, and so on. Other alkoxylated alcohols are formed by the reaction offatty acids and mono-, di- or polyhydric alcohols with an alkyleneoxide. For example, the reaction products of C.₆₋₃₀ fatty carboxylicacids and polyhydric alcohols which are monosaccharides such as glucose,galactose, methyl glucose, and the like, with an alkoxylated alcohol.Preferred are alkoxylated alcohols which are formed by the reaction ofstearic acid, methyl glucose, and and ethoxylated alcohol, otherwiseknown as PEG-20 methyl glucose sesquiisostearate.

Also suitable as the nonionic surfactant are alkyoxylated carboxylicacids, which are formed by the reaction of a carboxylic acid with analkylene oxide or with a polymeric ether. The resulting products havethe general formula disclosed in U.S. Patent Publication 2004/0180020A1published Sep. 16, 2004 paragraph [0172] incorporated herein byreference.

Other suitable nonionic surfactants include alkoxylated sorbitan andalkoxylated sorbitan derivatives. For example, alkoxylation, inparticular, ethoxylation, of sorbitan provides polyalkoxylated sorbitanderivatives. Esterification of polyalkoxylated sorbitan providessorbitan esters such as the polysorbates. Examples of such ingredientsinclude Polysorbates 20-85, sorbitan oleate, sorbitan palmitate,sorbitan sesquiisostearate, sorbitan stearate, and so on.

Also suitable as nonionic surfactants are silicone surfactants, whichare defined as silicone polymers, which have at least one hydrophilicradical and at least one lipophilic radical. The silicone surfactantused in the compositions of the invention are organosiloxane polymersthat may be a liquid or solid at room temperature. The organosiloxanesurfactant is generally a water-in-oil or oil-in-water type surfactantwhich is, and has an Hydrophile/Lipophile Balance (HLB) of 2 to 18.Preferably the organosiloxane is a nonionic surfactant having an HLB of2 to 12, preferably 2 to 10, most preferably 4 to 6. The HLB of anonionic surfactant is the balance between the hydrophilic andlipophilic portions of the surfactant.

Examples of silicone surfactants are those sold by Siltech LLC under theSilsurf tradename, Dow Corning under the tradename Dow Corning 3225CFormulation Aid, Dow Corning 190 Surfactant, Dow Corning 193 Surfactant,Dow Corning Q2-5200, and the like are also suitable. In addition,surfactants sold under the tradename Silwet by Union Carbide, andsurfactants sold by Troy Corporation under the Troysol tradename, thosesold by Taiwan Surfactant Co. under the tradename Ablusoft, those soldby Hoechst under the tradename Arkophob, are also suitable for use inthe invention. Such types of silicone surfactants are generally referredto as dimethicone copolyols or alkyl dimethicone copolyols.

Suitable cationic, anionic, zwitterionic, and amphoteric surfactants aredisclosed in U.S. Pat. No. 5,534,265, which is hereby incorporated byreference in its entirety.

H. Sunscreens

If desired, the compositions of the invention may contain 0.001-20%,preferably 0.01-10%, more preferably 0.05-8% of one or more sunscreens.A sunscreen is defined as an ingredient that absorbs at least 85 percentof the light in the UV range at wavelengths from 290 to 320 nanometers,but transmits UV light at wavelengths longer than 320 nanometers.Sunscreens generally work in one of two ways. Particulate materials,such as zinc oxide or titanium dioxide, as mentioned above, physicallyblock ultraviolet radiation. Chemical sunscreens, on the other hand,operate by chemically reacting upon exposure to UV radiation. Suitablesunscreens that may be included in the compositions of the invention areset forth on page 582 of the CTFA Cosmetic Ingredient Handbook, SecondEdition, 1992, as well as U.S. Pat. No. 5,620,965, both of which arehereby incorpated by reference. Further examples of chemical andphysical sunscreens include those set forth below.

1. UVA Chemical Sunscreens

The term “UVA sunscreen” means a chemical compound that blocks UVradiation in the wavelength range of about 320 to 400 nm.

Examples of suitable UVA sunscreen compounds of this general formulainclude 4-methyldibenzoylmethane, 2-methyldibenzoylmethane,4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane,2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane,4,4′diisopropylbenzoylmethane, 4-tert-butyl-4′-methoxydibenzoylmethane,4,4′-diisopropylbenzoylmethane,2-methyl-5-isorpoyl-4′-methoxydibenzoymethane,2-metyl-5-tert-butyl-4′-methoxydibenzoylmethane, and so on. Particularlypreferred is 4-tert-butyl-4′-methoxydibenzoylmethane, also referred toas Avobenzone. Avobenzone is commercial available from Givaudan-Roureunder the trademark Parsol 1789, and Merck & Co. under the tradenameEusolex 9020.

The claimed compositions may contain from about 0.001-20%, preferably0.005-5%, more preferably about 0.005-3% by weight of the composition ofUVA sunscreen. In one preferred embodiment of the invention the UVAsunscreen is Avobenzone, and it is present at not greater than about 3%by weight of the total composition.

2. UVB Chemical Sunscreens

The term “UVB sunscreen” means a compound that blocks UV radiation inthe wavelength range of from about 290 to 320 nm. A variety of UVBchemical sunscreens exist including .alpha.-cyano-.beta.,.beta.-diphenylacrylic acid esters as set forth in U.S. Pat. No. 3,215,724, which ishereby incorporated by reference in its entirety. Particularly preferredis Octocrylene, which is 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.Preferred is where the composition contains no more than about 10% byweight of the total composition of octocrylene. Suitable amounts rangefrom about 0.001-10% by weight. Octocrylene may be purchased from BASFunder the tradename Uvinul N-539.

Other suitable sunscreens include benzylidene camphor derivatives as setforth in U.S. Pat. No. 3,781,417, which is hereby incorporated byreference in its entirety.

Also suitable are cinnamate derivatives.

3. Physical Sunscreens

The composition may also contain one or more physical sunscreens. Theterm “physical sunscreen” means a material that is generally particulatein form that is able to block UV rays by forming an actual physicalblock on the skin. Examples of particulates that serve as solid physicalsunblocks include titanium dioxide, zinc oxide and the like in particlesizes ranging from about 0.001-50 microns, preferably less than 1micron.

J. Vitamins and Antioxidants

The compositions of the invention may contain vitamins and/or coenzymes,as well as antioxidants. If so, 0.001-10%, preferably 0.01-8%, morepreferably 0.05-5% by weight of the total composition are suggested.Suitable vitamins include ascorbic acid and derivatives thereof, the Bvitamins such as thiamine, riboflavin, pyridoxin, and so on, as well ascoenzymes such as thiamine pyrophoshate, flavin adenin dinucleotide,folic acid, pyridoxal phosphate, tetrahydrofolic acid, and so on. AlsoVitamin A and derivatives thereof are suitable. Examples are Vitamin Apalmitate, acetate, or other esters thereof, as well as Vitamin A in theform of beta carotene. Also suitable is Vitamin E and derivativesthereof such as Vitamin E acetate, nicotinate, or other esters thereof.In addition, Vitamins D and K are suitable.

Suitable antioxidants are ingredients which assist in preventing orretarding spoilage. Examples of antioxidants suitable for use in thecompositions of the invention are potassium sulfite, sodium bisulfite,sodium erythrobate, sodium metabisulfite, sodium sulfite, propylgallate, cysteine hydrochloride, butylated hydroxytoluene, butylatedhydroxyanisole, and so on.

K. Humectants

If desired, the compositions of the invention comprise about 0.01-30%,preferably about 0.5-25%, more preferably about 1-20% by weight of thetotal composition of one or more humectants. Suitable humectants includedi- or polyhydric alcohols such as glycols, sugars, and similarmaterials. Suitable glycols include alkylene glycols such as propylene,ethylene, or butylene glycol; or polymeric alkylene glycols such aspolyethylene and polypropylene glycols, including PEG 4-240, which arepolyethylene glycols having from 4 to 240 repeating ethylene oxideunits. Suitable sugars, some of which are also polyhydric alcohols, arealso suitable humectants. Examples of such sugars include glucose,fructose, honey, hydrogenated honey, inositol, maltose, mannitol,maltitol, sorbitol, sucrose, xylitol, xylose, and so on.

L. Other Botanical Extracts

It may be desirable to include one or more additional botanical extractsin the compositions. If so, suggested ranges are from about 0.0001 to10%, preferably about 0.0005 to 8%, more preferably about 0.001 to 5% byweight of the total composition. Suitable botanical extracts includeextracts from plants (herbs, roots, flowers, fruits, seeds) such asflowers, fruits, vegetables, and so on, including acacia (dealbata,farnesiana, senegal), acer saccharinum (sugar maple), acidopholus,acorus, aesculus, agaricus, agave, agrimonia, algae, aloe, citrus,brassica, cinnamon, orange, apple, blueberry, cranberry, peach, pear,lemon, lime, pea, seaweed, green tea, chamomile, willowbark, mulberry,poppy, and those set forth on pages 1646 through 1660 of the CTFACosmetic Ingredient Handbook, Eighth Edition, Volume 2.

M. Water Soluble Gellants

If the composition is in the emulsion form, it may be desirable toinclude other water soluble gellants in the water phase of thecomposition to provide thickening. Such gellants may be included a rangeof about 0.1-20%, preferably about 1-18%, more preferably about 2-10% byweight of the total composition is suggested, if present. Suitablegellants include soaps, i.e. salts of water insoluble fatty acids withvarious bases. Examples of soaps include the aluminum, calcium,magnesium, potassium, sodium, or zinc salts of C₆₋₃₀, preferably C₁₀₋₂₂fatty acids.

Also suitable are hydrocolloids such as gellan gum, gum arabic,carrageenan, and those set forth in U.S. Pat. No. 6,197,319 which ishereby incorporated by reference in its entirety.

N. Preservatives

The composition may contain 0.001-8%, preferably 0.01-6%, morepreferably 0.05-5% by weight of the total composition of preservatives.A variety of preservatives are suitable, including such as benzoic acid,benzyl alcohol, benzylhemiformal, benzylparaben,5-bromo-5-nitro-1,3-diox-ane, 2-bromo-2-nitropropane-1,3-diol, butylparaben, phenoxyethanol, methyl paraben, propyl paraben, diazolidinylurea, calcium benzoate, calcium propionate, captan, chlorhexidinediacetate, chlorhexidine digluconate, chlorhexidine dihydrochloride,chloroacetamide, chlorobutanol, p-chloro-m-cresol, chlorophene,chlorothymol, chloroxylenol, m-cresol, o-cresol, DEDM Hydantoin, DEDMHydantoin dilaurate, dehydroacetic acid, diazolidinyl urea,dibromopropamidine diisethionate, DMDM Hydantoin, and all of thosedisclosed on pages 570 to 571 of the CTFA Cosmetic Ingredient Handbook,Second Edition, 1992, which is hereby incorporated by reference.

O. Emulsion Stabilizers

If the composition of the invention is in the emulsion form, it may bedesirable to incorporate one or more emulsion stabilizers in thecomposition. If so, suggested ranges are about 0.0001-5%, preferablyabout 0.0005-3%, more preferably about 0.001-2% by weight of the totalcomposition. Suitable emulsion stabilizers include salts of alkali oralkaline earth metal chlorides or hydroxides, such as sodium chloride,potassium chloride, and the like.

III. Forms of the Cosmetic Compositions

The cosmetic compositions in accordance with the invention may be in avariety of forms include any type of cosmetic composition applied tokeratinous surfaces for the purpose of coloring, conditioning, orotherwise beautifying the keratinous surface.

A. Foundation Makeup Color Cosmetics

Foundation makeup or color cosmetics such as eyeshadow, blush,concealer, or eyeliner compositions in the liquid, cream, solid, orstick form. Suitable foundation makeup compositions may be water-in-oilor oil-in-water emulsions. Such compositions generally comprise about:

-   -   0.001-90% polyester silicone resin,    -   0.5-95% water,    -   0.5-25% particulate matter,    -   0.01-20% surfactant, and    -   0.1-95% nonvolatile or volatile oil.

In addition, these composition may further contain ingredients selectedfrom the group of humectants, preservatives, gellants, and all of theingredients as set forth above in the ranges set forth herein.

Various anhydrous color cosmetic products may also be suitable, such asblush, powder, lipsticks, eyeshadows, and the like. Such anhydrous colorcosmetic compositions may generally comprise about:

-   -   0.001-80% polyester silicone resin,    -   0.1-99% oil,    -   0.1-80% particulate matter; and optionally    -   0.001-50% thickening agent.

The compositions may additionally contain the various other ingredientsset forth above and in the ranges taught.

Preferably, the compositions are in the form of a lipcolor or lipstickwhich may be a composition for coloring the lips that is in liquid,semi-solid, or solid form.

Alternatively, the composition may be in the form of a base lip color,which is a lip color applied to the lips as a basecoat to provide color,followed by application of a separate gloss coat which comprises one ormore oils or waxes that provide shine, moisturization, or similarbenefits to the layers applied to the lips. Examples of such lipcompositions and topcoats are disclosed in U.S. patent application Ser.No. 2002/0159960, entitled “Method for Improving the Properties ofTransfer Resistant Lip Compositions and Related Compositions andArticles”, claiming priority from provisional application No.60/271,849, filed Feb. 27, 2001; which is hereby incorporated byreference in its entirety.

B. Lotions, Creams, Gels, and Sunscreens

The cosmetic compositions of the invention may be in the form oflotions, gels or sunscreens. Suitable skin care lotions and creams arein the emulsion form, and may be water-in-oil or oil-in-water emulsions,preferably oil-in-water emulsions. Creams, lotions, and/or may containthe following ranges of ingredients:

about 0.001-80% of the polyester silicone resin,

about 0.1-90% oil, and

about 0.01-20% surfactant.

C. Skin and Hair Cleansing and Conditioning Compositions

Skin and hair cleansing and conditioning compositions such as facialcleansers, shampoos, hair conditioners and the like are also suitablecosmetic compositions in accordance with the invention.

Generally skin and hair cleansing compositions comprise about:

-   -   0.001-90% of the polyester silicone resin,    -   1-95% water, and    -   0.1-40% surfactant, preferably an anionic, amphoteric, or        zwitterionic surfactant.    -   0.01-40% oil.

Suitable hair conditioner compositions comprise:

0.001-80% of the polyester silicone resin,

0.1-20% cationic surfactant,

0.1-30% fatty alcohol,

0.001-10% nonionic surfactant, and

5-95% water.

Suitable cationic and nonionic surfactants are as mentioned herein.Examples of suitable fatty alcohols include those having the generalformula R—OH, wherein R is a C₆₋₃₀ straight or branched chain, saturatedor unsaturated alkyl.

D. Nail Enamel Compositions

The cosmetically acceptable carrier for use may also comprise nailenamel compositions. Such compositions generally comprise:

0.001-90% of the polyester silicone resin,

0.01-80% solvent,

0.001-40% particulate matter, and

optionally 0.01-40% of one or more polymers such as cellulosic polymers,acrylate polymers, and the like.

Suitable solvents include acetone, alkyl acetates such as ethyl acetatebutyl acetate and the like, alkyl ethers such as propylene glycolmonomethyl ether, and the like.

The invention will be further described in connection with the followingexamples which are set forth for the purposes of illustration only.

EXAMPLES

Raw Materials Example Example 1 11 2 12 3 13 4 14 5 15 6 16 7 17 8 18 919 10 20 11 21 12 22 13 23 14 24 15 25 16 26

APPLICATIONS EXAMPLES

Non-limiting examples of the use in the resins of the present inventionin cosmetic lip care applications includes:

Cosmetic Applications-Lip % W/T Ingredient A B C D E F G H Phase AExample 1 99.30 Example 2 99.30 Example 3 99.30 Example 5 99.30 Example10 99.30 Example 16 99.30 Example 11 99.30 Example 8 99.30 Mica,Titanium Dioxide 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 Mica, TitaniumDioxide and Iron 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Oxides CalciumAluminum Borosilicate 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 TitaniumDioxide Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00PROCEDURE Mix all ingredients at room temperature with proper blending

Additional non-limiting examples of the use in the resins of the presentinvention in cosmetic lip care applications includes:

Cosmetic Applications-Eyes % W/T Ingredient A B C D E F G H Phase ACalcium Aluminium Borosilicate 25.00 25.00 25.00 25.00 23.00 23.00 23.0023.00 Iron Oxide 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 ManganeseViolet 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 Phase B Mica, TitaniumDioxide 12.00 12.00 12.00 12.00 12.00 12.00 12.00 12.00 Phase C Carnaubawax, beeswax 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 DipentaerythritylHexacapryllate/Hexacaprate 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00Isododecane, Quaternium- 18, Hectorite Propylene Carbonate, 4.00 4.004.00 4.00 4.00 4.00 4.00 4.00 Example 2 52.65 37.65 42.65 37.65 44.6539.65 44.65 39.65 Example 4 15.00 Example 6 10.00 Example 8 15.00Example 10 10.00 Example 12 15.00 Example 14 10.00 Example 16 15.00Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 1. Pre-mixPhase A in an osterizer. 2. Check the pigment dispersion 3. Repeat theprocess if needed. 4. Combine Phase C and heat to 80°-85° C. 5. AddPhase B to Phase C. 6. Add premixed Phase A to Phase B & C mixtures. Mixwell. 7. Maintain the temperature while mixing. 8. Add Phase D to thebatch and continue mixing. 9. Pour at 80°-75° C. in a mold.

In addition to their film forming properties, the resins of the presentinvention when applied to the skin have additional notable cosmeticproperties and can endow the makeup or care product with at least oneproperty chosen from properties of, for example, gloss, lubricity onapplication, comfort, color retention over time and after challenge,gloss retention over time, non-migration, outline definition and colorintensity.

The composition disclosed herein may, for example, constitute a makeupproduct for the body, lips or epidermal derivatives of humans which canhave properties of, for example, non-therapeutic treatment and/or care.In one embodiment, the composition disclosed herein constitutes alipstick or lip-gloss, a blusher or eye shadow, a tattooing product, amascara, an eyeliner, a nail varnish, an artificial tanning product forthe skin or a hair care or hair coloring product.

The present inventors have obtained, surprisingly, a compositioncomprising at least one resin described resulting in a film which isglossy, comfortable and does not migrate. Moreover, the composition'scolor intensity can be much better than that of the prior artcompositions.

The resins further exhibit effective dispersion of the pigments and/orfillers present in the composition; it does not exude when in stickform; it can have good properties of spreading and lubricity; and,moreover, it can endow the deposited film with sharply defined outlinesand with properties of effective gloss retention and color retentionover time (no color fading for at least three hours, uniformdisappearance of the makeup). It can be, furthermore, stable, forexample, for a number of months at ambient temperature (25° C. for morethan a year) and can also be stable to heat (47° C. for 2 months) and toultraviolet light without breakdown or odor over time.

FORMULATION EXAMPLES Formulation Example 1

An emulsion mascara composition was prepared as follows:

w/w % Materal 1.75 Acacia Senegal gum 2.25 Triethanolamine 0.20Lecithin/polysorbate 20/sorbitan laurate/propylene 0.20 Glycolstearate/propylene glycol laurate Simethicone 0.20 Hydroxyethylcellulose0.50 Panthenol 1.50 Nylon-12 0.30 Methylparaben 0.80 Polyethylene 9.00Iron oxides 3.00 Polysilicone 6 3.00 Isododecane 2.00 Nylon611/dimethicone copolymer/PPG-3 5.60 myristyl ether Stearic acid 10.80 Paraffin 2.80 Beeswax 2.30 Glyceryl stearate 1.00 Phenoxyethanol 0.10Propyl paraben 3.50 Carnauba wax 2.70 Cyclomethicone/dimethiconol 0.30Example 16 0.40 Hydrogenated polyisobutene/cyclomethicone Phytantriol0.60 Polyglycery-3 distearate/polysorbate 60/myristic acid/ {almiticacid/guar hydroxypropyltrimonium chloride/ tritcum vulgare (wheat) flourlipids/avocado oil QS100 Water

The composition was prepared by combining the water soluble pigments andwater phase and mixing well. The remaining oil phase ingredients wereseparately mixed. Both phases were combined and emulsified to form thefinal composition, which was a eyelash color in a rich black shade.

Formulation Example 2

A lipstick composition was prepared according to the following formula:

w/w % Materal 15.20 Example 15 18.40 Isostearyl alcohol 44.70Isododecane 13.70 Trioctyldodecyl citrate 8.00 Pigments and mica

The composition was prepared by combining the ingredients with heat andmixing well.

Formulation Example 3

A long wearing foundation makeup composition in the emulsion form wasprepared as follows:

w/w % Materal 19.50  Cyclomethicone/dimethicone copolyol 0.50 Sorbitansesquioleate 0.10 Propyl paraben 8.00 Titanium dioxide/methicone 0.10Silk powder 1.21 Mica/methicone 1.00 Iron oxides/methicone/boron nitride1.29 Iron oxides/methicone 2.00 Nylon-12 3.50 Boron nitride 1.00Dimethicone 5.00 Trimethylsiloxysilicate 9.00 Cyclomethicone 0.25 lauryldimethicone copolyol 0.05 Bisabolol 1.50 Tribehenin 0.50Nylon-611/dimethicone copolymer/PPG-3 myristyl ether Glyceryl rosinatein isododecane (44:56) 4.50 Example 14 1.00 Sodium chloride 0.01Tetrasodium EDTA 4.50 Butylene glycol 0.20 Methylparaben 3.00 SD-alcohol40B 0.35 Ethylene brassylate 0.10 Tocopheryl acetate 0.05 Retinylpalmitate Qs to 100 Water

The composition was prepared by combining the water phase ingredients.Separately the oil phase ingredients were combined. The two phases werecombined and mixed well to emulsify. The resulting foundation makeup waspoured into bottles.

Formulation Example 4

A lip gloss composition is made as follows:

w/w % Materal 4.00 Triisostearyl citrate 22.20  Diiosostearyl malate7.40 Octyldodecanol 8.10 Trioctyldodecyl citrate 1.50 Phenyltrimethicone 6.20 Polysilicone-6 12.30  Example 12 2.50 cyclomethicone0.40 Methylparaben 0.20 Propyl paraben 0.10 BHT 0.20 Benzoic acid 6 20Isododecane 12.30  Polybutene 7.10 Mica/titanium dioxide 1.40 Mica/ironoxides/titanium dioxide 4.80 Mica 4.30 Pigments

The composition is prepared by combining the ingredients with heat andmixing well. The resulting composition is a colored semi-solid.

Formulation Example 5

A face cream in the water and oil emulsion form is prepared as follows:

w/w % Materal 5.00 Glycerin 5.00 Xanthan gum 0.30 Trisodium EDTA 0.05Aloe Barbadensis leaf juice 0.50 Methylparaben 0.25 Butylene glycol 1.00Magnesium aluminum silicate 1.00 Magnesium ascorbyl phosphate 0.20Phenyl trimethicone 3.00 Tocopheryl acetate 1.00 Butylene glycoldicaprylate/dicaprate 9.00 Dimethicone 350 cst viscosisty 1.00 C12-15alkyl benzoate 5.00 Propylparaben 0.10 Phenoxyethanol 1.00 Cetyl alcohol4.00 Example 16 2.00 polyisobutene cyclomethicone Tetrahexyldecylascorbate 1.00 Glyceryl stearate/stearic acid/cetearyl 5.00alcohol/palmitoyl hydrolyzed wheat protein Qs to 100 Water

The composition is prepared by combining the oil phase and water phaseingredients separately, then mixing well to emulsify. The composition isof a creamy consistency.

Formulation Example 6

A sunscreen composition is prepared as follows:

w/w % Materal 6.00 Glycerin 5.00 Xanthan gum 0.30 Trisodium EDTA 0.05Aloe Barbadensis leaf juice 0.50 Methylparaben 0.25 Butylene glycol 1.00Magnesium aluminum silicate 1.00 Magnesium ascorbyl phosphate 0.20Phenyl trimethicone 3.00 Tocopheryl acetate 1.00 Butylene glycoldicaprylate/dicaprate 9.00 Dimethicone 350 cps visxosity 1.00 C12-15alkyl benzoate 0.50 Propylparaben 0.10 Phenoxyethanol 1.00 Cetyl alcohol4.00 Example 11 2.00 polyisobutene cyclomethicone 2.00 Oxybenzone 7.50Octinoxate 1.00 Tetrahexyldecyl palmitate 5.00 Glyceryl stearate/stearicacid/cetearyl QS 100 Water

The sunscreen composition is prepared by combining the oil phase andwater phase ingredients separately, then combining and mixing well toemulsify.

Formulation Example 7

A liquid composition suitable for use as eyeliner was made as follows:

w/w % Materal 7.00 Isododecane 19.60 Nylon 611/dimethicone copolymer/5.00 PPG-3 myristyl ether Polysilicone-6 25.00 Blue 1 lake 4.00 Red 40lake 3.60 Yellow 5 lake 0.80 Green 5 0.05 Silica 7.00Isododecane/quaternium-18 hectorite 25.80 propylene carbonate Dibutyladipate 2.95 Methylparaben 0.35 Dehydroacetic acid 0.20 Propyl paraben0.10 Sorbic acid 0.06 Example 16 5.50 isododecane

Formulation Example 8

A makeup remover composition was prepared as follows:

w/w % Materal 8.00 Butylene glycol dicaprylate/dicaprate 10.00  Example12 5.00 Phenoxyethanol 1.00 Propylparaben 0.10 Isododecane/quaternium-18hectorite/ 20.00  propylene carbonate Cetyl dimethicone copolyol 2.50Cyclomethicone 5.00 Butylene glycol 0.01 Trisodium EDTA 0.25Methylparaben QS 100 Water

The composition is prepared by separately combining the oil phaseingredients and the water phase ingredients, then mixing well toemulsify.

While the invention has been described in connection with the preferredembodiment, it is not intended to limit the scope of the invention tothe particular form set forth but, on the contrary, it is intended tocover such alternatives, modifications, and equivalents as may beincluded within the spirit and scope of the invention as defined by theappended claims.

1. A cosmetic composition comprising at least one silicone polyestermade by esterification reaction consisting of reacting: (a) dimer acidconforming to the following structure:

or hydrogenated dimer acid conforming to the following structure:

or mixtures thereof; with (b) a dimethicone copolyol conforming to thefollowing structure:

wherein; a is an integer ranging from 0 to 100; b is an integer rangingfrom 4 to 20, with the proviso that b is greater than a times 0.75; x isan integer ranging from 6 to 20; with the proviso that the ratio ofhydroxyl group to acid group be between 0.7 and 1.4. solvated ordispersed in a cosmetically acceptable carrier.
 2. (canceled) 3.(canceled)
 4. (canceled)
 5. (canceled)
 6. (canceled)
 7. (canceled) 8.(canceled)
 9. (canceled)
 10. (canceled)
 11. (canceled)
 12. (canceled)13. (canceled)
 14. (canceled)
 15. (canceled)
 16. (canceled) 17.(canceled)
 18. (canceled)
 19. (canceled)
 20. (canceled)